Basic pyrazolone monoazo dyes containing an ammonium or hydrazinium group

ABSTRACT

1-((+)K-Y-Z-),4-(K1-N=N-)-BENZENE A(-) BASIC DYES OF THE FORMULA WHEREIN K1 STANDS FOR A COUPLING COMPOUND OF TH PYRAZOLONE SERIES, Y STANDS FOR AN ALKYLENE OR ARYLENE RADICAL, Z STANDS FOR -O-, -S- OR -SO2-, K$ STANDS FOR A HYDRAZINIUM- OR AN AMMONIUM GROUP AND WHEREIN THE RING B MAY HEAR FURTHER SUBSTITUENTS; ARE USEFUL FOR DYEING ACRYLONITRILE POLYMERS AND COPOLYMERS. RESULTING DYEINGS HAVE GOOD FASTNESS PROPERTIES.

United States Patent Office 3,577,404 Patented May 4, 1971 ABSTRACT OF THE DISCLOSURE Basic dyes of the formula K stands for a coupling compound of the pyrazolone series, y stands for an alkylene or arylene radical, Z stands for -O, fiS or -SO K stands for a hydraziniumor an ammonium group and wherein the ring B may bear further substituents; are useful for dyeing acrylonitrile polymers and copolymers. Resulting dyeings have good fastncss properties.

wherein This invention relates to basic dyes of formula where R stands for a hydrocarbon or carboxylic acid amide radical, either of which may be substituted, or the cyano group, X for a hydrogen atom or a hydrocarbon radical which may be substituted, y for an alkylene or arylene radical, either of which may be substituted and which is attached to K through an optionally substituted alkylene radical or through a group of formula or -CH NHCO-CH Z for -O, -S- or -SO;, A for an anion equivalent to the dye cation, and K for a group of formula and where the aromatic ring B may be further substituted.

In Formula II and III R stands for an alkyl or cycloalkyl radical which may be substituted, or together with R and the N atom for a heterocycle, R for an alkyl or cycloalkyl radical which may be substituted, or together with R and the N atom for a heterocycle, R and R for hydrogen or identical or different alkyl or cycloalkyl radicals which may be substituted, R R and R each stands for an alkyl or cycloalkyl radical which may be substituted; R together with R and/ or R together with R and the N atoms adjacent to these substituents and R and R or R R and R together with the N atom may form heterocycles.

The dyes of Formula I can be produced by reacting a compound of formula )C (IV) where A represents the acid radical of an ester, with a 10 compound of formula R1 R3 R2 R4 (V) or s NgR,

1 I) The dyes of Formula I can alternatively be obtained by coupling the diazo compound of an amine of formula (VII) with a compound of formula HCCR HO-(l l N 1': (VIII) Dyes of Formula I in which R and R each represents an alkyl or cycloalkyl radical which may be substituted, or jointly with the adjacent N atom a saturated or partially saturated heterocycle, e.g. a piperidine, piperazine, pyrrolidine, morpholine or aziridine ring, can be arrived at by reacting, e.g. quaternating, a compound of formula with a compound of formula A group of good dyes, for example, conform to formula where Y represents an alkylene radical which may be substituted, the aromatic ring B may be further substituted,

the group -Z-Y K is in position 3 or 4, and R, X, Z,

A and K have the significances given in the foregoing.

Similarly good dyes correspond to formula (XII) Where Y represents an alkylene radical which may be substituted, the aromatic ring B may be substituted by alkyl, alkoXy, cyano, nitro, alkylsulphonyl, arylsulphonyl, carbonyl or trifluoromethyl or halogen, and R, X, Z, A and K have the aforestated meanings.

where arylene stands for an arylene radical which may be substituted, e.g. a phenylene, naphthylene or tetrahydronaphthylene radical, X for an alkylene radical which may be substituted or a radical of formula the aromatic ring B may be further substituted and R, X, Z, A and K bear the meanings given them above.

The anion A in the dyes of Formula I can be replaced by other anions with the aid of an ion exchange or by reaction with salts or acids, of necessity in more than one stage, e.g. via the hydroxide. It is desirable for the dyes to be free from sulphonic acid groups. Particularly good dyes are obtained, for example, when X denotes a phenyl radical which may be substituted and R, a hydrocarbon radical which may be substituted, e.g. an alkyl radical, e.g. the methyl group.

Similarly good dyes result when y has the significance of a radical of formula and Z is an oxygen atom. Examples of the optionally substituted hydrocarbon radical are alkyl, aryl and cycloalkyl radicals, e.g. a phenyl, naphthyl, tetrahydronaphthyl or cyclohexyl radical. If these radicals are substituted they contain, for example, a hydroxyl group, a halogen atom, the cyano group or an aryl radical. In each instance halo gen represents preferably chlorine or bromine.

The aryl or arylene radicals may be substituted by alkoxy goups. The alkyl or alkoxy radicals generally bear 1 to 6 or preferably 1 to 4 carbon atoms.

The carboxylic acid phenyl amide radical is an example of a substituted carboxylic acid amide radical. The alkylene radical may be straight or branched; optionally it contains 1 to 10 or preferably 1 to 6 carbon atoms and it may be substituted, e.g., by a hydroxyl group.

In most instances Z represents an oxygen atom. The aromatic ring B, or B where present, may be substituted by an alkyl, alkoxy, cyano, nitro, alkylsulphonyl, arylsulphonyl, carbonyl or trifiuoromethyl group or by a halogen atom.

When neither R nor R stands for a hydrogen atom, the radicals R to R represent optionally substituted alkyl radicals, such as optionally substituted methyl, ethyl, propyl or butyl radicals, or cycloalkyl radicals, such as cyclohexyl radicals. If these radicals are substituted they contain in particular a hydroxyl group, a halogen atom, the cyano or a phenyl group.

In conjunction with the adjacent N atom the radicals R and R may form a heterocycle, e.g. a pyrrolidine, piperazine, morpholine, aziridine or piperidine ring. The radical R jointly with R and/or the radical R together with R and the N atoms adjacent to these substituents, may form a saturated or unsaturated, preferably fiveor six-membered heterocycle, for example a pyrazolidine, pyridazine or pyrazoline ring such as a trimethylenepyrazolidine or tetramethylenepyrazolidine ring.

The radicals R to R represent optionally subsituted alkyl radicals, e.g. optionally substituted methyl, ethyl, propyl or butyl radicals, or cycloalkyl radical such as cyclohexyl radicals. If these radicals are substituted they contain in particular a hydroxyl group, a halogen atom, the cyano or a phenyl group.

The radicals R and R jointly with the adjacent N atom, may form a heterocycle, for example a pyrrolidine, piperidine, morpholine, aziridine or piperazine ring.

The radicals R to R together with the adjacent N atom, may form a heterocycle, e.g. a group of formula or may stand for a pyridine ring.

The acid radicals A are preferably those of hydrohalic acids; A stands preferably for C1 or Br, Other acid radicals A are for example those of sulphuric acid, a sulphonic acid or of hydrogen sulphide.

The anion A may be an organic or inorganic ion, e.g. a halogen ion, such as chlorine, bromine or iodine, or methylsulphate, sulphate, disulphate, perchlorate, phosphate, phosphotungstic molybdate, benzenesulphonate, naphthalenesulfonate, 4-chlorobenzene sulphonate, oxalate, maleinate, acetate, propionate, methanesulphonate, chloracetate or benzoate, or complex anions such as zinc chloride double salts. The reaction of a compound of Formula IV with a compound of Formula V or VI is effected preferably in an organic solvent at temperatures of 50 to +250 C., preferably at 10 to +120 C.

The reaction can alternatively be carried out in aqueous medium, if necessary with the addition of an organic solvent, or in the absence of solvent at the aforestated temperatures.

The coupling reaction of the diazotized compounds of Formula VII with compounds of Formula VIII generally takes place in alkaline medium with cooling, e.g. at (l-5 C. It can however be effected in acid, e.g. acetic acid, medium.

The reaction of a compound of Formula IX with a compound of Formula X is conducted preferably in an inert solvent, or if necessary in aqueous suspension, or in the absence of solvent in an excess of a compound of Formula X, at elevated temperatures and if necessary in the presence of a buffer.

Examples of compounds of Formula X are alkyl halides, e.g. methyl or ethyl chloride, bromide and iodide, alkylsulphates such as dimethylsulphate, and acrylic amideshydrochloride, e.g. CH =CHCONH /HCl, epoxides, epichlorohydrins, etc.

The new dyes are employed for dyeing and printing filaments, fibres and textiles made therefrom which consist wholly or in part of acrylonitrile polymers or copolymers. They are used further for the mass coloration of plastics, for paper dyeing in the heater and for leather dyeing. v

The dyes of this invention, provided they are present as salts of inorganic or organic acids that form approximately neutral solutions in water, are dyeable from weakly alkaline, neutral or weakly acid baths. It is advisable to dye from an acid bath, either by setting the bath at the start wtih a suitable acid such as acetic, formic, tartaric, sulphuric or naphthalenesulphonic acid, alkali bisulphate or an acid alkali phosphate, or by adding an agent to the bath which produces acid during the dyeing process. Examples of such agents are the salts of volatile bases of strong non-volatile acids, such as ammonium sulphate, and the water soluble esters of organic acids which saponify during dyeing, such as the methyl or ethyl esters of aliphatic oxy acids, e.g. lactic, malic and tartaric acids. If the dyes are applied in mineral acid solution, as is the case with betain-like compounds, the mineral acid also can be neutralized during dyeing by the gradual addition of alkaline salts of weaker acids, e.g. sodium acetate. The dyes are applicable with heating in open baths and in enclosed machines at temperatures above C. under pressure.

Under the normal dyeing conditions as described, the

6 baths are largely exhaused in normal dyeing times, and diazotized with 6.9 parts of sodium nitrite. The ice cold level, usually very bright dyeings are obtained which have diazo solution is neutralized and combined with a fine good light and wet fastness and pH stability. aqueous suspension of 18.8 parts of 1-(2'-methylphenyl)- The dyeing obtained further have good fastness to 3-methyl-5-pyrazolone at The isolated, dried dye is washing, water, sea water, perspiration, sublimation, dissolved in 700 parts of boiling chlorobenzene, and after cross dyeing, decatizing, pressing, bleaching, dry cleanthe addition of 25 parts of dimethyl sulphate the solution ing and solvents. is boiled for an hour with reflux. On cooling to room The dyes are well soluble in water and have good power temperature the precipitated water soluble dye is collected of buildup. They are suitable for combination and in on a filter, washed with petroleum ether and purified by mixture with other dyes give excellent dyeings. They recrystallization. This dye is suitable for application to reserve wool. polyacrylonitrile fibres, on which it gives very fast yellow In Belgian Patent 633,447 the dye of formula dyeings.

1 in. PTO-( N (:1

is described, which among other uses is employed for Very similar dyes having equally good properties are dyeing polyacrylonitrile fibres. The dyes of Formula I arrived at when the procedure of this example is followed,

show better power of build-up on polyacrylonitrile fibres using in place of the 18 parts of 2-amino-2'-dimethylfrom baths of Permutit prepared water and are highly aminophenylethyl ether 18 parts of 3-amino-2-dimethylstable in Permutit water. amino-phenylethyl ether, or in place of the 18.8 parts of In the following examples the parts and percentages are 1-(2'-methylphenyl)-3-methyl-5-pyrazolone 20.9 parts of by weight and the tempeartures in degrees centigrade. 1-(2-ch1orophenyl)-3-methyl-5-pyrazolone.

EXAMPLE 1 EXAMPLE 4 17.2 parts of 4-amino-2'-chlorophenyl-ethyl, prepared The compound 4-(4'-aminophenoxy)-benzyl-N,N-diby reducing 4-nitro-2-chlorophenyl-ethyl ether by the methyl-hydrazinium chloride is prepared by reaction of known method, are dissolved in 150 parts of 6% hydro- 4 (4' acetaminophenoxy)-benzylchloride with asymchloric acid and diazotized at 0 with an aqueous solumetrical dimethyl hydrazine in toluene solution and subsetion of 6.9 parts of sodium nitrite. The diazo solution is quent saponification to the amino compound. 29.3 parts neutralized and united with a fine ice-cold suspension of of this chloride are diazotized with 6.9 prats of sodium 19 parts of 1-phenyl-3-methyl-5-pyrazolone in 150 parts nitrite in 200 parts of ice-cold 6% hydrochloric acid. of water, on which coupling takes place. The dye settles The neutralized diazo solution is then combined with a out and is collected on a filter. solution, likewise neutral and cooled to 0, of 11 parts of 35.7 parts of the chlorine containing monoazo dye (a) 3-metl1yl-5-pyrazolone in 100 parts of water. Stirring is thus obtained are dissolved in 400 parts of toluene at 80. continued at 0 until the coupling reaction is complete. 6.6 parts of asymmetrical dimethyl hydrazine are added The dye is isolated and purified by the known methods. to the solution, the reaction temperature is raised at 95 It is suitable for dyeing polyacrylonitrile fibres in very over one hours and this temperature is held for several fast yellow shades. hours with stirring until the reatcion is complete. The A dye having the same good properties is obtained when solution is then cooled to room temperature and the the procedure of Example 4 is followed, with the 29.3

precipitated dye filtered off. This new water soluble dye parts of 4-(4 amino phenoxy)-benzyl-N,N-dimethylcan be purified by recrystallization. It is suitable for dyehydrazinium chloride replaced by 35 parts of the amino ing polyacrylonitrile fibres in very fast yellow shades. compound of formula e9 (CHz)zI|l-CHg-CO-NH CHz-OOC NHZ o1 NHz EXAMPLE 2 5 EXAMPLE 5 A dye very similar to that of Example 1 and with 48.5 parts of the dye of formula 01 or: c1 cH2c112on-cHz0-C -N=N-p-poO-NH-O Cort .l

equally good properties is obtained when the chlorine which is produced by coupling diazotized l-(4'-amino- 2', containing dye (a) produces by the procedure of that 5-dichlorophenoxy) 3 chloropropanol (2) with 5- example is reacted with dimethylamine in toluene at pyrazolone-3-carboxylic acid anilide, are entered into 250 -80 and the resulting dye quaternated with dimethyl-. parts of a 3% aqueous N,N-dimethylhydrazine solution sulphate at 100-105 at room temperature. After stirring for 1 hour at this temperature the reaction mixture is raised to 85 over 3 EXAMPLE 3 hours and is held at 85-95 for 6 hours with reflux. The

18 parts of 2-amino-2-dimethylamino-phenylethyl ether dye formed is isolated by known methods. It dyes polyare dissolved in 200 parts of 6% hydrochloric acid and acrylonitrile fibres in fast yellow shades.

7 DYEING EXAMPLE 20 parts of the dye of Example 1 and 80 parts of dex- TABLE A.-Continued trin are ground in a ball mill for 48 hours. One part of Kw represents H o the preparation obtamed 1s pasted with 1 part of 40% acetic acid solution, 400 parts of distilled water are run CH over the paste and the Whole is boiled for a short time. 3 It is then diluted with 7000 parts of distilled water, with K11 represents C2H4OH the final addition of 2 parts of glacial acetic acid. 100 N(0H3)2 parts of polyacrylonitrile fabric, previously treated for -15 minutes at 60 c. in 20 minutes, held at the boil 10 repesmts E for 1 hour, and the fabric then well rinsed. A yellow dye- P I I ing good light wet fastness properties is obtained. CZHE In the following table, details are given of the struc- K m resents C H tural composition of further dyes which can be produced p 5 by the procedures of Examples 1 to 5. PMCHW The symbols K y, Z, R and X in the formula K14 represents H 6 69 3 2 -N K y--Z 4 B 1 -N=No-o-R HO-C A K15 represents X ,have the meanings given them in the table. The anion A may be any one of those named in the specification. The represents PMCHW] symbol K stands for any one of the radicals K -K listed NHQ in Table A below. In a given dye these group ngs may K" represents N(C2H5)2] be exchanged for any one of the other groupings here given. 3

TABLE A 0 K13 represents [IIT(C2H4OH)2] K may stand for any one of the symbols K K NHZ which represent the following groupings: K represents CH2-CH2 TABLE A N l K] represents [N(CH3)3I CH2CH2 K2 represents [N(Czl1 )3] NH K; represents- (ilHa K represents CH2CH2 [N(C2H5)2] [-N CH2] K4 represents [N(C2H4OH);1 CH2 CH2 K represents $11 H [N(C2H40H)2] K2 represents CH2CH2 K6 represents CH2--CH2 [N/ O] IL/OH2OH2\ intone-CH2 CHz-CHz K22 represents [N(C2H5CN)2] K1 represents l: j 1 11 K23 represents CH2 KB represents -N H CH2 CH2 i NN CH3 K represents CH2 CH2 CH2 CH3 TABLE Position of K -y-Z-group in ring B and significa tion of K99, y, and Z or of K93 and y jointly with Z Posi- Substltuent in ring Shade of dyeing tion K9 y Z B and position R X on acrylic fibre 2 K1 CH2OHz- O- CH3 H Greenish yellow. 2 K2 Same as above O Same as above H Do. 2 d do H D0. 2 H Do. 2 H DO- 2 H D0- 2 H D0- 2 H Do. 2 do -CH3 Do. 2 1 J10 Same as above Do. 2 K15 ......do.... do ("in do D v V TABLE'C0ntinued Position of K -y-Z-group in ring B and signification of K y, and Z or of K and y jointly with Z Ex. Posl- Substituent in ring Shade of dyeing N0. tion K y Z B and position R X on acrylic fibre 2 K do do "fi Do. 2 .do do Do. 2 dn (10 DO- 2 do... do Do. 2 C O-NH2 H Yellow. 2 Same as above H Do. 2 ..do H Do. 2 H Do. 2 .do H Do. 2 do H Do. 2 fin H D0- 2 -CONH2 H Do. 2 Same as above H Do. 2 (10.... H Do.

2 K CHz-(|JHCHz- 0- on H Do.

32.. 2 K Same as above -O d H Do. 33. 2 Km -O-- (In H Do.

34, 2 K -0H2CH2- O --C0 :4 Beddlsh yellow.

2 Same as above Same as above Do. 7 2 do do Do. 2 d0 0---- Do. 2 fin (10 D0- 2 5-cl1loro do do Do. 2 dn fin Do.

2 s (in do Do.

2 CH 2 Same as above 2 do 2 do 2 do- 2 dn 2 K OHz(|1HOHz- -s-- on 49 2 K CH OH2 -s do.. --cm D0.

2 K Same as above S Same as above Do; 2 d do do Do. 2 .do do Do. 2 lo ..do Do.

2 Do. 2 Do. 2 Do. 2 Do.

60 2 Km do S-]T ..do Same as above Do.

Cl 2 1 do -s- -do I CH l 7 l 2 Same as above Do. 2 do Do. 2 Reddlsh yellow. 2 Do. 2 ..do Do. 2 Do.

TABLE-Con'tinued Position of K -y-Z-group in ring B and signification of K y, and Z or of K and y jointly with Z Ex. Posi- Substituent in ring Shade of dyeing N 0. tion K y Z B and position R X on acrylic fibre 73"-.. 2 K" Sameasabove "-0- do ..CONHC2H4OH Do.

74 2 O 4-SO2-N(CH )2 CH3 H Do. 75 2 O 4S OzN(CH3)z Same as above H Do.

76... 2 K1 --do --o- 4-s02oH3 1o :00.

77. 2 K1; ...do O Same as above .do Same as above D0.

0 O OH 78 2 K1 ..d0 O- d0 d0 D0.

5-S OzN(CH3)2 .do Sam; as above Do.

Same as above do Reddish yellow.

Same as above Do. Greenish yellow. Same as above o.

w DIMWNWNWWWWOJN mmmmmmmmmmm Reddish yellow.

... -do ..do Same as above Do. do Do.

1 do d -CH2CH2 YGHOW. Same as above (1 Beddish yellow.

Do. H Do. -CH3 D0.

K1 --CH-(|3HCH2 -O- do do Same as above Do.

K Same as above -S do do do. Do. do -SO2- do... 0 Do. Km d0 S0zdo Do.

-oH2-om- -0- -0H3 Yellow.

Same as above 0: WWWWOJOJWWMWNWWWWWODNMWWWWOJNOQOJ Same as above Do. do Do. H Do.

K5 -CH2CIHCHZ- O v 110 Do.

133-- 4 K5 Same as above O (10 Same as above Do.

a wu s TABLE-Conltinued Position of K -y-Z-gr up in ring B and signification of K y, and Z or of K and y jointly with Z Ex. Posi- Substituent in ring Shade of dyeing N 0. tion K Y Z B and position R X on acrylic fibre 135-.-. 4 KB Same as above do Same as above Do. 136 4 9 0 do do Do. 137 4 Km (10 -CH D0. 138-.-- 4 Kn do. OHa Do.

139.--. 4 K12 on 0 on Do.

140.-.- 4 do Same as above Do. 141..-. 4 .do do Do. 142"" 4 ,do do Do. 143"" 4 do Do. 144... 4 do Do. 145 4 do do Do. 146.--. 4 A H 0. 147-.-. 4 do H Do.

4 Same as above Do. 4 do Do, 4 H Do. 4 H Do. 4 H Do. 4 H Do. 4 H Do. 4 H D0. 4 H Do.

168.--- 4 H Do.

159-. 4 H Same as above Do. 160...- 4 H -d Do. 161 4 H d0 Do. 162.- 4 C ONHz do.. Reddish yellow. 163 4 Same as above do o. 164...- 4 H Yellow. 165...- 4 do H Do.

166-..- 4 Ki CH2?HCH2- so'r- CH; lCl Do.

167 4 K Same as above- SO Same as above Same as above Do. 168.... 4 K1 .do S 3-ch1oro do H Do.

169...: 4 Km ---.-d0 S- do D0.

170 4 K do S 3SOrCHa do H Do.

171 4 Km do S Same as above do Do.

172 4 K1 .do S .....de C0NH2 Same as above Do. 173..-- 4 K10 (1O S ""110 C O-NHz H D0,

Position of K -y-Z-group in ring B and signification of K y, and Z or of K and y jointly with Z Substituent Shade of Ex. Poslin ring B dyeing on No. tio K9 Y j y with Z and DOSitlOIl R X acrylic fibre "-0113 2 K2 Same as above Sameas above Same as above- Do. 2 K do do Do. 2 K4 D0. 2 K Do. 2 Ku Do. 2 K7 D0. 2 K8 Do. 2 Kn Do. 2 K Do. 2 K11 Do. 2 Km Do. 2 K13 Do. 2 K14 D0. 2 K D0. 2 K15 Do. 2 K11 Do. 2 K13 D0. 2 Km Do. 2 K Do. 2 K22 D0. 2 K23 Do. 2 K23 Do. 2 K1 D0. 2 K2 d0 do H D TABLEC0nltinued Position of K -y-Z-gr0up in ring B and signification of K y, and Z or of K and y jointly with Z Substituent Shade of Ex. Posiin ring B dyeing on No. tion K y jointly with Z and position R X acrylic fibre 199...- 2 H Do. 200,-.. 2 H Do- 201.... 2 H D0. 202...- 2 H D0. 203...- 2 H Do. 204.-.. 2 11 Do. 205..-- 2 H Do. 206-..- 2 H Do. 207...- 2 H D0. 208 2 H D0. 209.... 2 H D0. 210-... 2 H Do. 211...- 2 H D0. 212--.. 2 H Do. 213.-.. 2 H D0. 214. 2 H Do. 215...- 2 H Do. 216-... 2 H Do.

218-..- 2 H D0. 219.-.. 2 H D0.

221.-.. 2 Km Same as above ..do H Do.

222.--- 2 K1 --..-do .-do Do.

223. 2 K -....do ..do Same as above...... Do.

---H2? 224.... 2 K H3cs02 ..do -.do Do.

225...- 2 Do. 226.-.. 2 D0. 227-... 2 D0. 228.-.. 2 D0. 229-... 2 D0. 230. 2 Do. 231.... 2 Same as above-. Do. 232. 2 K -do ..dO H D0. 233---- 2 Km d0.. .dO H Do. 234. 2 K ...-.do.. CH3 H Do. 235-... 2 Same as above-- CH; Do. 236 2 Same as above Do. 237- 2 0 Do. 238...- 2 D0. 239.... 2 Do. 240-... 2 Do.

241---. 2 K1 -H2C-O 3-chloro- -.do Do.

242.... 2 K Same as above Same as above ..do I Do. 243---- 2 K1 -....do 3-SO2CH3 Do. 244.... 2 K ...-.do.. Same as above.-... D0. 245.... 2 K1 ..-..do. -SO2N(CH3)2 Do. 246.... 2 K .....do Same as above ..do ..do Do.

241--.; 2 K1 CHz-CONHOHz-O ..L.-. .do H 7 Do.

248.... 2 Do. 249-... 2 Do. 250.... 2 D0.

252..-. 2 Km ....-do ..do Same as above.- Do.

253--.- 3 K1 H3O--SO2- .-do H Do.

254.-.. 3 K1 Same as above CH3 H Do. 255.... 3 do Same as above.- H D0. 266.--- 3 do CO-NH2 H Do. 257 3 .do Same as above-. H Do. 2 3 ..do 6-01 -OH H Do, 259 3 do Same as above-..- Same as above.. H Do.

260.... a K. 0H,-s ..do H Do.

TABLE-Continued Position of K -y-Z-group in ring B and signification oi K y, and Z or of K and y jointly with Z Substituent Shade 0! Ex. Posiin ring B dyeing on N 0. tion K y jointly with Z and position R X acrylic fibre 261..-- 3 K1 Same as above. do H Do. 262.-.- 3 K do H Do. 263---- 3 K1 -C O-NH: H D0. 264..-- 3 K10 Same as above.- H Do.

265.--- 3 K1 n CH; Do.

266..-- 3 Km Same as above.. Same as above Do.

267---- 3 K1 cnzodo do 3 do do Do, 3 do do Do, 3 do do Do, 3 do do Do, 3 do do Do, 3 do do Do. 3 do do Do, 3 do do D0. 3 do do Do. 3 do do DO. 3 do do Do. 3 do do Do. 3 do do Do. 3 do ,do Do. 3 do do Do. 3 do do D0- 3 do do Do. 3 do do Do. 3 do do Do. 3 do do Do. 3 do do Do. 3 do do Do. 3 do H DO. 3 do H D0. 3 do H D0. 3 do H Do. 3 do H D0. 3 do H D0. 3 do H D0. 3 do H Do. 3 do H D0. 3 do H DO. 3 do H D0. 3 do H DO. 3 do H DO. 3 do H D0- 3 do H D0. 3 do H D0. 3 do H D0. 3 do H D0. 3 ..do H D0. 3 do H D0. 3 do H D0. 3 do H D0. 3 do H D0.

313.... 3 K1 CHz-CONHCHz-O ..do H Do.

314.... 3 K Same as above... do H Do.

315...- 3 K1 do on Q Do.

316---. 3 Km do do H Do.

311-.-. 3 K1 CHzCONHCH-S ..do H Do.

318.... 3 Km Same as above. do H Do. 319.... 3 K1 do do H D0. 320---- 3 K15 do do H D0- 321-..- 4 K1 -CH2O --do H D0.

322..-. 4 K, same as abov do H Do. 323.-.- 4 K3 do H D0. 324..-. 4 K4 do H DO. 325.--. 4 K5 do H D0. 326.--- 4 Kl do H D0. 327.--- 4 K7 do H D0. 328.-.- 4 Kg do H D0. 329-... 4 Kg do H Do. 330..-- 4 K10 do H D0. 331-.-- 4 K11 do H D0. 332..-- 4 Km o H D0. 333..-. 4 Km .....(10 do H D0. 334.. 4 K14 fl do H D0- 335...- 4 K15 do do H Do. 336-..- 4 Km do H Do. 337.-.- 4 K11 0 do H D0. 338.... 4 Km do H Do. 339--.- 4 Km do do H Do.

TABLE continued Position of K -y-Z-group in ring B and signification of K y, and Z or of K and y jointly with Z Ex. Posi- Substitllellt in g Shade of dyeing- No. tion K y jointly with Z B and position R X on acrylic fibre 340..-- 4 K10 an H D0. 341-.-- 4 K21 H D0. 342-.-- 4 K22 dn (10 H D0- 343..-. 4 K n (in H Do.

344.--- 4 K1 fin fin Do.

4 Same as above Do. 4 (in D0- 4 Do. 4 (in D0- 4 (in D0- 4 do Do. 4 (10.... Do. 4 .do Do. 4 (10-... Do. 4 (in D0- 4 do Do- 4 (in D0- 4 do Do. 4 (In D0- 4 (in D0. 4 do Do. 4 (In D0- 4 (in D0. 4 do Do. 4 .do.. Do. 4 do Do. 4 do Do.

367.--- 4 K --OHz-C o-NH-cm-o- -.e H Do.

368.--. 4 K Same as above. do H Do.

369---. 4 K1 do do Do.

370.--. 4 Km do I Same as above. Do.

371---- 4 K1 OHz -.d0 H Do.

372..-- 4 K Same as abovedo H Do.

373.... 4 K mfln Do.

374.-.- 4 K do...- dn Same as above D0. 375.--- 4 K10 dn do Do,

376..-- 4 11, -CHa-SO2 fin do 377.... 4 K Same as above. do dn Do. 378-.-- 4 K1 do do H D0,. 379..-. 4 Km do do H D0- 380...- 4 K CHz-O 3-011101'0 -.-..do H Do.

381..-- 4 Same as above Same as above .-do H Do. 382.-.- 4 d0 fin dn H D0- 383..-- 4 min (in H D0- 384..-- 4 do fin H D0.

385...- 4 0- ...--do ..do..... H Do.

4 K Same as above- .dn fln H Do. 4 K1 fin 3-502-0113 do H Do. 4 Km (in Same as above do H Do. 4 K1 do (in H D0. 4 Km do H Do.

391---- 4 K1 an 110 Do.

392...- 4 K dn .fln Same as above Do- 393. 4 K; (In fin --cm Do. 7

4 4 Km ""1 do Same as above Do. 395-..- 4 K do (in H D0. 396-.-- 4 Km do do H D0. 397.--- 4 K1 d0 OONH1 H D0. 398...- 4 K4 -dn Same as above- H D0- 399-". 4 Km fln dn H D0- TABLECutinued Position of K -y-Z-group in ring B and signification of K9, y, and Z or of KEB and y jointly with Z Ex. Posi- Substituent in ring Shade of dyeing N0. tion K95 y jointly with Z B and position R X on acrylic fibre 400.--. 4 K1 o do Reddish yellow;

401m. 4 Km do do Same as above Do.

l 402.--- 4 K1 CH2-NHCOCH -O- -CH Yellow 4 K2 Same as above--- Same as above Same as above Do. 4 do dn do Do. 4 do do Do. 4 -dn H D0- 4 rin H D0. 4 ,do H Do. 4 H Do. 4 do H Do. 4 do H D0. 4 -do H Do. 4 do H Do. 4 do.-.. H De. 4 Jlfi H Do. 4 .do H Do. 4 do H Do. 4 do H Do. 4 (in H D0. 4 ...do H Do. 4 do 11 Do. 4 dn H DO. 4 do H Do. 4 fin H Do.

EXAMPLE 425 EXAMPLE 174 The compound 4-(2'-amino-4'-chlorophenoxy)-benzyl- N,N-dirnethylhydrazinium chloride is prepared by reac- H 1% tion in chlorobenzene solution of 4-(2'-acetamino-4- O- chlorophenoxy)-benzyl chloride with dimethylhydrazine r s)2 '-H2 C19 and subsequent saponification to the amino compound, 32.8 parts of this compound are diazotized in dilute icecold hydrochloric acid by the known method. After neutralization of the diazo solution with sodium carbonate an ethyl alcohol solution of 19 parts of 1-pheny1-3-methyl-5- O pyrazolone is added at 0 and stirring is continued at this 4 EXAMPLE 189 temperature until the coupling reaction is complete. The dye thus formed settles out. It is collected on a filter, dried ll HO N and ground, whereupon it 1s obtained as a yellow powder 3; which is applicable to acrylic fibres. On these fibres it f- 9 gives fast yellow dyeings.

Dyes with very similar, equally good properties are obtained when the 38.2 parts of 4-(2-amino-4'-chlorophenoxy)-benzyl-N,N-dimethylhydrazinium chloride employed in this example are replaced by the equivalent EXAMPLE 425 amount of 4-(2'-amino-4'-chlorophen0xy)-benzyl-N,N-trimethylammonium chloride or by 4-(2'-amino-4'-chloro- O phenoXy)-benzyl-pyridinium chloride, or again when the l] it 19 parts of 1-phenyl-3-methyl-5-pyrazolone are replaced I by 11 parts of 3-rnethy1-5-pyrazolone, the process of pro- (CHQZIIT-HZCO-O C19 duction being otherwise exactly as described in the above.

Formulae of representative dyes of the foregoing examples are as follows:

EXAMPLE 1 C 6O Having thus disclosed the invention what we claim is:

I ll 1. Basic dye of the formula NHz HOC\ /N N 019 K z 110-0 1-i A F EXAMPLE 4 X e; wherein 'ahN-CHrO-C 3 R is a member selected from the group consisting of IlIHZ 1, Q; 019 (a) substituted or unsubstituted hydrocarbon, (b) carboxamide, (c) carboxylic acid hydroxyethylarnide, (d) carboxylic acid phenylamide, (e) cyano and (f) H hydrogen;

X is a member selected from the group consisting of hydrogen and substituted or unsubstituted hydrocarbon;

y is a member selected from the group consisting of (a) unsubstituted or hydroxy-substituted alkylene having from 1 to 6 carbon atoms and (b) unsubstituted or alkoxy-substituted arylene; bound to K by a bridge selected from the group consisting of unsubstituted or hydroXy-substituted alkylene having from 1 to 6 carbon atoms,

Z is O-, -S-- or -'SO A is an anion [equivalent to the dye cation]; K is a group of the formula R is a member selected from the group consisting of alkyl, substituted alkyl, cyclohexyl, substituted cyclohexyl and, together with R and the nitrogen atom to which both are bound, a heterocycle; any substituent of the substituted alkyl or substituted cyclohexyl being selected from the group consisting of hydroxy, halo, cyano and phenyl; the heterocycle being a member selected from the group consisting of pyrrolidine, piperazine, morpholine, aziridine and piperidine;

R is a member selected from the group consisting of alkyl, substituted alkyl, cyclohexyl, substituted cyclohexyl and, together with R and the nitrogen atom to which both are bound, a heterocyclic; any substituent of the substituted alkyl or substituted cyclohexyl being selected from the group consisting of hydroxy, halo, cyano and phenyl; the heterocycle being a member selected from the group consisting of pyrrolidine, piperazine, morpholine, aziridine and piperidine;

each of R and R is, independently, a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, cyclohexyl and substituted cyclohexyl; any substituent of the substituted alkyl or substituted cyclohexyl being selected from the group consisting of hydroxy, halo, cyano and phenyl;

each of R R and R is, independently, a member selected from the group consisting of, alkyl, substituted alkyl, cyclohexyl and substituted cyclohexyl; any substituent of the substituted alkyl or substituted cyclohexyl being selected from the group cOnsisting of hydroxy, halo, cyano and phenyl;

or R R and 'R are together with the nitrogen atom to which each is bound, a member selected from the group consisting of pyridinium and monoquaternized triethylenediarnine;

or R and R are together with the nitrogen atom to which both are bound, a heterocycle selected from the group consisting of piperidine, piperazine, pyrrolidine, morpholine and aziridine;

or R with R and the respective nitrogen atoms to which they are bound is a saturated or unsaturated 5- or 6- membered heterocycle, each ring member of which is carbon, nitrogen or oxygen;

or R with R and the respective nitrogen atoms to which they are bound is a saturated or unsaturated 5- or 6-membered heterocycle, each ring member of which is carbon, nitrogen or oxygen;

and wherein aromatic ring B is either further unsubstituted or is further substituted, any substituent thereon being a or of the formula member selected from the group consisting of alkyl, alkoxy, cyano, nitro, alkylsulphonyl, arylsulphonyl, carbonyl, trifluoromethyl and halo; hydrocarbon being a member selected from the group consisting of alkyl, aryl and cyclohexyl; any substituent on a substituted hydrocarbon being a member selected from the group consisting of hydroxy, halo, cyano and aryl; each alkyl and each alkoxy having from 1 to 4 carbon atoms; and each aryl and the aryl of each arylene being a member selected from the group consisting of phenyl, naphthyl and tetrahydronaphthyl.

2. Basic dye according to claim 1 wherein y is unsubstituted or hydroxy-substituted alkylene having from 1 to 6 carbon atoms, Z is in one of the 3- and 4-positions on ring B, and any heterocycle of R with R or R with R is a member selected from the group consisting of pyrazolidine, pyridazine and pyrazoline.

3. Basic dye according to claim 1 wherein y is unsubstituted or hydroxy-substituted alkylene having from 1 to 6 carbon atoms, Z is in the 2-position on ring B, and any heterocycle of R; with R or R with R is a member selected from the group consisting of pyrazolidine, pyridazine and pyrazoline.

4. Basic dye according to claim 1 wherein y is unsubstituted or alkoxy-substituted arylene and any heterocycle of R with R or R with R is a member selected from the group consisting of pyrazolidine, pyridazine and pyrazoline.

5. Basic dye according to claim 1 wherein X is substituted or unsubstituted hydrocarbon, the hydrocarbon is phenyl, R is methyl, and any heterocycle of R with R or R with R is a member selected from the group consisting of pyrazolidine, pyridazine and pyrazoline.

6. Basic dye according to claim 1 wherein y is paraphenylene, the bridge is a member selected from the group consisting of and any heterocycle of R with R or R with R is a member selected from the group consisting of pyrazolidine, pyridazine and pyrazoline.

7. Basic dye according to claim 1 in which Z is O.

8. The basic dye according to claim 1 of the formula 9. The basic dye according to claim 1 of the formula 10. The basic dye according to claim 1 of the formula 25 26 11. The basic dye according to claim 1 of the formula References Cited UNITED STATES PATENTS 2,128,255 8/1938 Krzikalla et a1. 260163X 9 2,128,256 8/1938 Krzikalla et a1. 260-156X z)Z Z -C N 019 2,140,944 12/1938 Schirm 260-156 l 2,224,112 12/1940 Krzikalla et 51. 260 156 2,476,986 7/1949 Martin 260-156X 2,633,461 3/1953 Seidenfaden et a1. 260-207X 3,170,910 2/1965 Neracher et a1. 260-156X 3,252,965 5/1966 Entschel et a1. 260-152X 12. The basic dye according to claim 1 of the formula FLOYD D. H'IGEL, Primary Examiner C1 N=NC--CCH3 HO-(.17 1'3 US. 01. X.R. l 8-4, 7, 13,41; 117-138.8, 142, 154; 260-37, 152, 155,

G3 a)2 HzC- 6 

